Amidrazones and their use as pesticides

Abstract: The present invention is concerned with amidrazones, insecticidal amidrazone compositions, and methods of using such compositions.

Description: The present invention is concerned with amidrazones, pesticidal (e.g. insecticidal) amidrazone compositions, and methods of using such compositions. The search for compounds which have a combination of excellent insecticidal activity and low undesirable toxicity is a continuing one because of factors such as the desire for compounds exhibiting greater activity, better selectivity, low undesirable environmental impact, low production cost, and effectiveness against insects resistant to many known insecticides. EP-A-0 261 755 and EP-A-0 347 216 disclose insecticidal N'-substituted-N,N'-diacylhydrazines. However, neither of these documents disclose or suggest the specific amidrazones to which the present invention is directed. In particular, neither EP-A-0 261 755 nor EP-A-0 347 216 discloses or suggests compounds diacylkydrazine compounds wherein the nitrogen atom of one of the hydrazine groups bears a =O group and the nitrogen of the other hydrazine group bears a -NR 1 ,R 2 group wherein R 1 and R 2 are alkyl. Compounds of the present invention have utility for controlling plant-destructive pests (e.g. insects) in crops of cultivated plants, ornamentals, and forestry. According to the present invention, there is provided a compound having the formula wherein A and B are each independently aryl or aromatic heterocyclyl, optionally substituted with one or two substituents selected from (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, halo, halo(C 1 -C 6 )alkyl and nitro; U is oxygen; Y is NR 1 R 2 , wherein: (a) R 1 and R 2 are alkyl; or (b) R 1 and R 2 together with the nitrogen atom to which they are attached form a 5- or 6- membered ring; and (c) Z is a straight or branched (C 3 -C 9 )alkyl; or an agronomically acceptable salt of such compound. Further, in accordance with the present invention, there are provided compositions containing compounds of the present invention, and methods of using such compounds and compositions. In the following definitions, unless stated otherwise, the alkyl and alkoxy, groups may, optionally, be substituted with one or more substituent selected from halo such as fluoro, chloro or bromo, cyano, nitro, alkyl such as methyl, and mixtures thereof. Preferably, "(C 1 -C 6 )alkoxy" is methoxy, ethoxy, n -propoxy, iso propoxy, n -butoxy, sec -butoxy, iso butoxy or t -butoxy. "(C 1 -C 6 )alkyl" means straight and branched (C 1 -C 6 )alkyl groups, preferably methyl, ethyl, n -propyl, iso propyl, n -butyl, iso butyl, s -butyl, t -butyl or n -pentyl. "Aromatic Heterocyclyl" is a fully unsaturated five or six membered heterocyclic ring containing one, two or three heteroatoms independently selected from oxygen, nitrogen or sulfur with the remaining ring atoms being carbon atoms. Preferred are furyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, oxazolyl, pyrrazolyl, imidazolyl, triazolyl, thienyl, and thiazolyl. The heterocyclyl ring is optionally substituted by one or two substituents independently selected from nitro; (C 1 -C 6 )alkyl, preferably methyl or ethyl; halo(C 1 -C 6 )alkyl, preferably trifluoromethyl; (C 1 -C 6 )alkoxy, preferably methoxy; and halo, preferably chloro. "Aryl" is an aromatic (C 6 -C 16 )carbocyclic structure, preferably an unsaturated monocyclic or bicyclic(C 6 -C 10 )carbocyclic structure, more preferably phenyl or naphthyl. The aryl group is optionally substituted by one or two substituents independently selected from nitro; (C 1 -C 6 )alkyl, preferably methyl or ethyl; halo(C 1 -C 6 )alkyl, preferably trifluoromethyl; (C 1 -C 6 )alkoxy, preferably methoxy; and halo, preferably chloro. "Halo" means bromo, chloro, fluoro and iodo; "halogen" is bromide, chloride, fluoride and iodide. "Halo(C 1 -C 6 )alkyl" is preferably trifluoromethyl, 2-chloroethyl or 2-bromoethyl. "Agronomically acceptable salts" include acid addition salts, preferably hydrochloride, sulfate, and bisulfate; metal salts, preferably sodium, potassium, calcium and magnesium; ammonium salts, preferably isopropylammonium; and trialkylsulfonium salts, preferably trimethylsulfonium. "Pesticidally effective amount" means the amount of active substance sufficient to exert the desired pest control, preferably causing a significant reduction compared to a control group of either the pest population or crop damage inflicted by such pest population, more preferably causing a twenty-five percent reduction, even more preferably at least ninety percent reduction. In certain cases the compounds of this invention possess asymmetric centers which give rise to optical enantiomorphs and diastereomers. This invention includes such enantiomorphs and diastereomers. In one preferred embodiment, A and B are each phenyl independently optionally substituted by one or two substituents independently selected from halogens, preferably bromo, alkoxys, preferably methoxy, and alkyls, preferably methyl and ethyl. Preferably A is 4-substituted phenyl, more preferably 4-bromophenyl or 4-ethylphenyl. Preferably B is phenyl or 3,5-dimethylphenyl. Also in this preferred embodiment, Z is a branched (C 4 -C 7 )alkyl, preferably tert -butyl, tert -amyl, or neo -pentyl; U is oxygen; and Y is 1-morpholino, 1-piperidino or di(C 1 -C 3 )alkylamino, preferably dimethylamino. Accordingly, a preferred compound is a compound wherein A and B are each phenyl independently optionally substituted by one or two substituents independently selected from halogens, methyl and ethyl, Z is a branched (C 4 -C 7 )alkyl, U is oxygen, and Y is 1-morpholino, 1-piperidino, or di(C 1 -C 3 )alkylamino. A more preferred compound is a compound wherein A is 4-bromophenyl or 4-ethylphenyl; B is phenyl or 3,5-dimethylphenyl; Y is 1-morpholino, 1-piperidino or dimethylamino; and Z is t -butyl. Preferred compounds are N-(4-bromobenzoyl)-morpholine N'-benzoyl-N'- t butylhydrazone; N-(4-bromobenzoyl)-morpholine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone; N,N-dimethylbenzamide-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone; N-(4-ethylbenzoyl)-morpholine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone; N-(4-ethylbenzoyl)-piperidine- N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone; and N-(4-ethylbenzoyl))-pyrrolidine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. The following Table lists examples of compounds of the present invention, but are not intended as limitations on the invention. The compositions and compounds of this invention can be applied directly to the locus to be protected, as for example, the area around or upon economic plants infected with pests or to plants on which infestation is to be prevented. The compounds and compositions may be used either as contact or systemic pesticides. In the practice of the method of the invention, the active compound may be applied to the soil or foliage where it is absorbed by the plant, translocated to other plant parts and ultimately ingested by the pest (e.g. insects) by means of ingestion of the plant part(s). This means of application is referred to as "systemic" application. Alternatively, the active compound may be applied to the soil and contacted therein with the insects and other pests to be controlled. This means of application is referred to as "soil" application. In another alternative, the active compound may be foliarly applied to the plants to be freed from insects and other pests which feed on the foliage. The compounds of the present invention can be used in the form of compositions or formulations. Examples of the preparation of compositions and formulations can be found in the American Chemical Society publication "Pesticidal Formulation Research," (1969), Advances in Chemistry Series No. 86, written by Wade Van Valkenburg; and the Marcel Dekker, Inc. publication "Pesticide Formulations", (1973) edited by Wade Van Valkenburg. In these compositions and formulations, the active substance is mixed with inert, agronomically acceptable (i.e., plant compatible and/or pesticidally inert) diluents or extenders, for example conventional inert, agronomically acceptable pesticide diluents or extenders, such as solid carrier material or liquid carrier material, of the type usable in conventional pesticide compositions or formulations. An agronomically acceptable carrier is any substance which can be used to dissolve, disperse or diffuse the active ingredient in the composition without impairing the active ingredients effectiveness and which by itself has no significant detrimental effect on the soil, equipment, desirable plants, or agronomic environment. If desired, adjuvants such as surfactants, stabilizers, antifoam agents and antidrift agents may also be combined. Examples of compositions and formulations according to the invention are aqueous solutions and dispersions, oily solutions and oil dispersions, pastes, dusting powders, wettable powders, emulsifiable concentrates, flowables, granules, baits, invert emulsions, aerosol compositions and fumigating candles. Wettable powders, pastes, flowables and emulsifiable concentrates are concentrated preparations which are diluted with water before or during use. Baits are preparations generally comprising a food or other substance attractive to insects, that includes at least one compound of the present invention. The invert emulsions are mainly used for air application, where large areas are treated with a comparatively small amount of preparation and may be prepared in the spraying apparatus shortly before, or even during, the spraying operation by emulsifying water in an oil solution or an oil dispersion of the active substance. Compositions and formulations may be prepared in a known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants such as conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents. When water is used as diluent, organic solvents may be added as auxiliary solvents. The active compounds of the present invention may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, and/or synergists. In the compositions of the invention, the active compound is typically present in an amount from about 0.0001-99% by weight. For compositions suitable for storage or transportation, the amount of active ingredient is preferably from about 0.5-90% by weight, and more preferably from about 1-75% by weight, of the mixture. Compositions suitable for direct application or field application generally contain the active compound in an amount from about 0.0001-95%, preferably from about 0.0005-90% by weight, and more preferably from about 0.001-75% by weight, of the mixture. The active compounds can be applied as pesticidal sprays by methods commonly employed, such as conventional high-gallonage hydraulic sprays, low gallonage sprays, ultra-low-volume sprays, airblast spray, aerial sprays, and dusts. The present invention also contemplates methods of controlling pests (e.g. insects) which comprises contacting pests with a combative or toxic amount (i.e. a pesticidally effective amount) of at least one active compound of the invention alone or together with a carrier vehicle (composition or formulation) as noted above. The term "contacting", as employed herein, means applying to at least one of (a) such pests and (b) the corresponding habitat thereof (i.e., the locus to be protected, for example, to a growing crop or to an area where a crop is to be grown) the active compound of this invention alone or as a constituent of a composition or formulation. In addition to the aforementioned ingredients, the compositions according to the invention may also contain other substances commonly used in compositions of this kind. For example, a lubricant, such as calcium stearate or magnesium stearate, may be added to a wettable powder or to a mixture to be granulated. Furthermore there may, for example, be added adhesives such as polyvinylalcohol-cellulose derivatives or other colloidal materials, such as casein, to improve the adherence of the pesticide to the surface to be protected. Compositions and formulations according to the present invention may also include known pesticidal compounds. The following known insecticidal, fungicidal and acaricidal compounds are suitable for use in such a combined preparation: acephate, acethion, acetoxon, aldicarb, aldoxycarb, aldrin, allethrin, allyxycarb, alpha-cypermethrin, amidithion, amitraz, amlure, anethol, azethion, azinphosethyl, azinphos-methyl, azocyclotin, bacillus thuringiensis, BCPE, bendiocarb, bensultap, benzoximate, benzyl acetate, benzyl benzoate, BHC, bifenthrin, binapacryl, bomyl, BPMC, bromophos, bromophos-ethyl, bromopropylate, bufencarb, buprofezin, butacarb, butocarboxim, butonate, butoxycarboxim, calcium arsenate, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chlordane, chlordecone, chlordimeform, chlorfenethol, chlorfenson, chlorfensulphide, chlorfenvinphos, chlormephos, chlorobenzilate, chloropropylate, chlorphoxim, chlorpyrifos, chlorpyrifos methyl, chlorthiophos, clofentezine, CPCBS, CPMC, crotoxyphos, crufomate, cryolite, cufraneb, cyanofenphos, cyanophos, cyanthoate, cyfluthrin, cyhexatin, cypermethrin, cyphenothrin, cyromazine, DAEP, DDT, DDVP, deltamethrin, demeton, demeton-S-methyl, demeton-O-methyl, demeton-S, demeton-S-methyl sulfoxid, demephion-O, demephion-S, dialifor, diazinon, dicapthon, dichlofenthion, dicofol, dicrotophos, dieldrin, dienochlor, diflubenzuron, dihydrorotenone, dimefox, dimetan, dimethoate, dimethrin, dinex, dinitrophenol,dinobuton, dinocap, dioxabenzofos, dioxacarb, dioxathion, disparlure, disulfoton, DMCP, DNOC, d-trans allethrin, endosulfan, endothion, endrin, entice, EPBP, EPN, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprop, etrimfos, fenamiphos, fenazaflor, fenbutatin-oxide, fenitrothion, fenoxycarb, fenpropathrin, fenson, fensulfothion, fenthion, fenvalerate, flubenzimine, flucythrinate, fluenethyl, flufenoxuron, fluvalinate, fonofos, formetanate hydrochloride, formothion, fosmethilan, fosthietan, furathiocarb, furethrin, grandlure, heptachlor, HETP, hexythiazox, hydramethylnon, hydroprene, IPSP, isazophos, isobenzan, isofenphos, isoprocarb, isoprothiolane, isothioate, isoxathion, jodfenphos, kinoprene, lead arsenate, leptophos, lethane, lindane, lythidathion, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methyl parathion, methyl phencapton, mevinphos, mexacarbate, MIPC, mirex, monocrotophos, MTMC, naled, nicotine, nonachlor, omethoate, ovex, oxamyl, oxydeprofs, oxydisulfoton, oxythioquinox, paraoxon, parathion, paris green, permethrin, perthane, phencapton, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, plifenate, profenofos, promecarb, propargite, propetamphos, propoxur, prothidathion, prothiophos, prothoate, PTMD, pyridaben, pyridaphenthion, quinalphos, resmethrin, ronnell, rotenone, ryania, s-bioallethrin, salithion, schradan, sodium fluosilicate, sophamide, sulfotepp, sulprofos, tefluthrin, temephos, TEPP, terbufos, tetrachlorvinphos, tetradifon, tetramethrin, tetrasul, thallium sulfate, thiocarboxime, thiocyclamhydrogenoxalate,thiometon, tolclofos-methyl, toxaphene, triazophos, trichlorfon, trichloronate, triflumuron, trimethacarb, vamidothion and xylylcarb. Fungicides which can be combined with the insecticides of this invention also include: (a) dithiocarbamate and derivatives such as ferbam, ziram, maneb, mancozeb, zineb, propineb, metham, thiram, the complex of zineb and polyethylene thiuram disulfide, dazomet, and mixtures of these with copper salts; (b) nitrophenol derivatives such as dinocap, binapacryl, and 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; (c) heterocyclic structures such as captan, folpet, glyodine, anilazine, ditalimfos, 4-butyl-1,2,4-triazole, 5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole, etradiazole, dithianon, thioquinox, benomyl, thiabendazole, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, vinclozolin, iprodione, procymidone, triadimenol, triadimefon, bitertanol, prochloraz, fenasimol, bis-(p-chlorophenyl)-3-pyridinemethanol, bis-(p-chlorophenyl)-5-pyrimidinemethanol, triarimol, flutriafol, flusilazole, propiconazole, ectaconazole, myclobutanil, alpha-[2-(4-chlorophenyl)ethyl]-alpha-phenyl-1H-1,2,4-triazole-1-propanenitrile, hexaconazole, cyproconazole, terbuconazole, diniconazole, fluoroimide, pyridine-2-thiol-1-oxide, 8-hydroxyquinoline sulfate and metal salts thereof, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, cis-N-[(1,1,2,2-tetrachloroethyl)thiol]-4-cyclohexene-1,2-dicarboximide, cycloheximide, dehydroacetic acid, captafol, ethirimol, quinomethionate, D,L-methyl-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)alanine methyl ester, D,L-methyl-N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone, D,L-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-(3,5-dichlorophenyl)-5-methyl-5-(methoxymethyl)-1,3-oxazolidi-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide, fenpropimorph, fenpropidine, 2,6-dimethyl-N-tridecylmorpholine, dodemorph, and triforine; (d) miscellaneous halogenated fungicides such as chloranil, dichlone, chloroneb, tricamba, TCPN, dichloran, 2-chloro-1-nitropropane, polychloronitrobenzenes such as pentachloronitrobenzene (PCNB), and tetrafluorodichloroacetone; (e) fungicidal antibiotics such as griseofulvin, kasugamycin, polyoxin, validamycin, and streptomycin; (f) copper-based fungicides such as copper hydroxide, cuprous oxide, basic cupric chloride, basic copper carbonate, copper terephthalate, copper naphthenate and Bordeaux mixture; and (g) miscellaneous fungicides such as dodine, phenylmercuric acetate, N-ethylmercuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide, phenylmercuric monoethanol ammonium lactate, p-dimethylaminobenzene sodium sulfonate, methyl isothiocyanate, 1-thiocyano-2,4-dinitrobenzene, 1-phenylthiosemicarbazide, nickel-containing compounds, calcium cyanamide, lime sulfur, thiophanate-methyl, flutolanil, edinophos, isoprothiolane, propenazole, and tricyclazole. The compounds of this invention may be prepared by a variety of reaction schemes. The following Examples exemplify preparations for the compounds of Table I above, and for intermediates of such compounds, but are not intended to be limits thereon. Example A: Preparation of the intermediate N- t -butyl-N-(3,5-dimethylbenzoyl)-hydrazine. To a 3 liter flask fitted with mechanical stirring and a reflux condensor was charged 160 g (1.28 mole) t -butyl hydrazine hydrochloride, 160 ml (8.89 mole) of water and 108 g (1.35 mole) of 50% sodium hydroxide solution in water. Slowly 100g (1.72 mole) acetone was added and stirred 1 hour. The reaction mixture was diluted with 600 ml methylene chloride and followed by a careful addition of a mixture of 120g (1.5 mole) 50% sodium hydroxide in 120g of ice. To the reaction mixture was then added 169 g (1.0 mole) of 3,5-dimethylbenzoyl chloride dropwise over 1.75 hours and stirred an additional hour 500 ml of water containing 5 ml of concentrated hydrochloric acid was added to the reaction and the entire mixture was transferred to a separatory funnel, washed twice more with 300 ml water each, dried over anhydrous magnesium sulfate, and concentrated in vacuo to yield 298 g (1.14mole) of a pale yellow oil. The 298 g of pale yellow oil isolated above, 600 ml of toluene, 400 ml of water and 5.0 g (0.056 mole) of oxalic acid were charged to a 3 liter flask fitted with a mechanical stirrer and Dean Stark trap and refluxed 5 hours. During this time fresh toluene and water were added to replace that lost by draining the Dean Stark trap. The reaction mixture was neutralized with dilute sodium hydroxide and washed with brine one time quickly. The product, which precipitated upon cooling to room temperature, was filtered and triturated with hexanes. Obtained was 153 g of white solid, mp 125°-127°C. Example B - Preparation of N-(4-bromobenzoyl)-morpholine-N'-benzoyl-N'- t butylhydrazone. a: N-(4-bromothiobenzoyl)-morpholine. To 40 g (460 mmole) of morpholine was added 18.56 g (100 mmole) of 4-bromobenzaldehyde and 4.08 g (125 mmole) of elemental sulfur. The solution was refluxed for 15 minutes. The reaction mixture was poured onto water and extracted with 1 liter of ethyl acetate. The ethyl acetate extract was washed with brine, dried over anhydrous magnesium sulfate, evaporated in vacuo , then triturated with ethyl ether/hexanes to yield 26.9g of the product, mp 135°-137°C. b: 1-(4-bromobenzoyl)-morpholine-N'- t -butylhydrazone. To 5.0 g (18.7 mmole) of N-(4-bromothiobenzoyl)-morpholine prepared in Example B (a) was added 12.5 g (142 mmole) of anhydrous t -butyl hydrazine. The mixture was heated at reflux (bath temp. ∼160°C) for 6 hours, stirred at room temperature over the weekend, then refluxed for an additional 8 hours. The reaction mixture was cooled to room temperature, diluted with methylene chloride and washed with water. The methylene chloride solution was dried over anhydrous magnesium sulfate, evaporated in vacuo and triturated with ethyl ether/hexanes. The soluble fraction contained the product contaminated with ∼10% starting material. c: N-(4-bromobenzoyl)-morpholine-N'-benzoyl-N'- t -butylhydrazone. To 2.0 g (6.2 mmole) of 1-(4-bromobenzoyl)-morpholine N'- t -butylhydrazone in 15 g of methylene chloride was added 0.5 g (6.0 mmole) of anydrous sodium bicarbonate, 10 ml (6.0 mmole) of 5% sodium bicarbonate solution in water, and 0.95g (6.8 mmole) of benzoyl chloride. The two phase solution was stirred 15 minutes at room temperature, separated, dried over anhydrous magnesium sulfate then evaporated in vacuo . The crude product crystallized out of hexanes at -5°C and was chromatographed on silica in 1:1 ethyl ether/hexanes to yield the desired product, mp 119°-121°C. Example C - Preparation of N-(4-bromobenzoyl)-morpholine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. By substantially following the procedure of Example B, using 3,5-dimethyl benzoyl chloride in place of benzoyl chloride, 2.0g of the desired product was obtained, an oil. ( nmr (CDCl 3 ) δ 1.4 9H s, 2.3 6H s, 3.2 4H bs, 3.6 4H m, 6.6-7.5 7H m). Example D - Preparation of N,N-dimethyl-4-ethylbenzamide-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. a: N,N-dimethyl-4-ethylbenzamide. In 50 g of water was dissolved 36.0 g (442 mmole) of dimethylamine hydrochloride. 50 g of ice and 36 g (450 mmole) of 50% sodium hydroxide solution were added. While maintaining the internal temperature below 10°C, 35 g (208 mmole) of 4-ethylbenzoyl chloride was added. The mixture was stirred 20 minutes, extracted with ethyl ether, dried over anhydrous magnesium sulfate and concentrated in vacuo to yield 36.2 g of N,N-dimethyl-4-ethylbenzamide. b: N,N-dimethylimmonium-4-ethylbenzoyl chloride chloride. 3.5 g (19.8 mmole) of N,N-dimethyl-4-ethylbenzamide prepared in Example D (a) and 3.0 g (25 mmole) of thionyl chloride were dissolved in 6 g of methylene chloride and refluxed 4 hours. The reaction mixture was evaporated in vacuo and triturated with ethyl ether/hexanes to yield 2.5 g of product. c: N,N-dimethyl-4-ethylbenzamide-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. In 10 ml of methylene chloride was dissolved 2.5 g (10.8 mmole) of N,N-dimethylimmonium-4-ethylbenzoyl chloride chloride obtained in Example 3(b) and 2.5 g (11.4 mmole) of N- t -butyl-N-(3,5-dimethylbenzoyl)-hydrazine obtained from Example A. Upon adding 2.5 g (24.7 mmole) of triethylamine dropwise an exotherm was observed. The reaction was stirred 30 minutes, concentrated in vacuo and partitioned between ethyl ether and 1 M sodium hydroxide solution. The ethyl ether layer was dried over anhydrous magnesium sulfate, concentrated and chromatographed on silica gel in 1:1 ethyl ether:hexanes yielding 2.0 g of an oil. (nmr (CDCl 3 ) δ 1.2 3H t, 1.4 9H s, 2.3 6H s, 2.6 2H q, 2.8 6H s, 6.6-7.2 7H m). Example E - Preparation of N-(4-ethylbenzoyl)-morpholine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. a: N-(4-ethylbenzoyl)-morpholine. To a cooled solution of 9.6 g (0.11 mole) of morpholine in 25 ml methylene chloride was added 8.4 g (0.05 mole) of 4-ethylbenzoyl chloride dropwise. The reaction mixture was stirred 30 minutes and a white precipitate formed. The mixture was washed three times each with 25 ml of water, dried over anhydrous magnesium sulfate and evaporated in vacuo to yield 10.6 g of yellow oil. b: N-morpholininum-4-ethylbenzoyl chloride chloride. To a solution of 1.1 g (5.0 mmole) of N-(4-ethylbenzoyl)-morpholine, obtained from Example E (a), in 10 ml of methylene chloride was added 2.5 g (20.0 mmole) of oxalyl chloride. The mixture was stirred one hour then concentrated in vacuo to yield 1 g of a solid residue. c: N-(4-ethylbenzoyl)-morpholine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. 1.0 g (5.0 mmole) of N- t -butyl-N-(3,5-dimethylbenzoyl)-hydrazine obtained in Example A and 1.0 g (10.0 mmole) of triethylamine were dissolved in 10 ml methylene chloride and cooled in an ice water bath. To this mixture, was added dropwise over 3 minutes a solution of 1.0g of N-morpholininum-4-ethylbenzoyl chloride chloride obtained in Example E (b) in 30 ml of methylene chloride and stirred for 5 minutes. The reaction mixture was washed 3 times each with 50 ml of water, dried over anhydrous magnesium sulfate, concentrated in vacuo and chromatographed on silica in 1:4 ethyl acetate:hexanes to yield the desired product, a pale yellow oil (nmr (CDCl 3 ) δ 1.2 3H t, 1.4 9H s, 2.3 6H s, 2.8 2H q, 3.2 4H bs, 3.6 4H m, 6.6-7.3 7H m). Example F - Preparation of N-(4-ethylbenzoyl)-piperidine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. By substantially following the procedure of Example E, replacing morpholine with piperidine, the desired product was obtained, an off-white solid mp-100°-102°C. Example G - Preparation of N-(4-ethylbenzoyl)-pyrrolidine-N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. By substantially following the procedure of Example E, replacing morpholine with pyrrolidine, the desired product was obtained, a light yellow solid mp-109°-110°C. On the basis of their strong initial pesticidal activity and excellent residual pesticidal activity, compounds according to the invention may be used in low dosages in controlling pests. The amount of dosage for a given situation can be routinely determined and depends on a variety of factors, for example, the substance used, the kind of pest, the formulation used, the state of the crop infested with the pest and the prevailing weather conditions. In general, for the control of pests in agriculture and horticulture, a dosage corresponding to from about 0.1 grams to about 1000 grams of the active substance per hectare may be used, and from about 5 grams to about 200 grams per hectare of the active substance is preferred. Representative pests which can be controlled by the compounds of the present invention include: American Cockroach ( Periplaneta americana ), Bean Leaf Beetle ( Cerotoma trifurcata ), Bean Leaf Roller ( Urbanus proteus ), Black Carpenter Ant ( Camponotus pennsylvanicus ), Black Cutworm ( Agrotis ipsilon ), Boll Weevil ( Anthonomus grandis grandis ), Colorado Potato Beetle ( Leptinotarsa decemlineata ), Fall Armyworm ( Spodoptera frugiperda ), German Cockroach ( Blattella germanica ), Green June Beetle ( Cotinis nitida ), House Cricket ( Acheta domesticus ), Housefly ( Musca domestica ), Mexican Bean Beetle ( Epilachna varivestis ), Potato Leaf Hopper ( Empoasca fabae ), Red Harvester Ant ( Pogonomyrmex barbatus ), Red Imported Fire Ant ( Solenopsis invicta ), Redlegged Grasshopper ( Melanopus femurrubrum ), Southern Armyworm ( Spodoptera eridania ), Southern Corn Rootworm ( Diabrotica undecimpunctata howardi ), and Tobacco Budworm ( Heliothis virescens ). It has been found, by biological evaluation, that compounds according to the present invention have pesticidal activity and are capable of controlling larvae and adult forms of pests, especially insects from the order Lepidoptera. One skilled in the art will know how to determine the activity of a given compound against a given insect and the dosage required to obtain general or selective pesticidal effects.

Claims: A compound having the formula wherein A and B are each independently aryl or aromatic heterocyclyl, optionally substituted with one or two substituents selected from (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, halo, halo(C 1 -C 6 )alkyl and nitro; U is oxygen, Y is NR 1 R 2 , wherein: (a) R 1 and R 2 are alkyl; or (b) R 1 and R 2 together with the nitrogen atom to which they are attached form a 5- or 6- membered ring; and (c) Z is a straight or branched (C 3 -C 9 )alkyl, or an agronomically acceptable salt of such compound. A compound as claimed in claim 1, wherein: A and B are each phenyl independently optionally substituted by one or two substituents independently selected from halogens, methyl and ethyl; Z is a branched (C 4 -C 7 )alkyl; U is oxygen; and Y is 1-morpholino, 1-piperidino, or di(C 1 -C 3 )alkylamino. A compound as claimed in claim 2, wherein: A is 4-bromophenyl or 4-ethylphenyl; B is phenyl or 3,5-dimethylphenyl; Y is 1-morpholino, 1-piperidino or dimethylamino; and Z is t -butyl. A compound as claimed in claim 1, wherein R 1 and R 2 , together with the nitrogen atom to which they are attached form a piperidino, morpholino or pyrrolidino ring, A compound as claimed in claim 1 selected from: N-(4-bromobenzoyl)-morpholine N'-benzoyl-N'- t -butylhydrazone; N-(4-bromobenzoyl)-morpholine N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone; N,N-dimethylbenzamide N'-(3, 5-dimethylbenzoyl)-N'- t -butylhydrazone; N-(4-ethylbenzoyl)-morpholine N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone; N-(4-ethylbenzoyl)-piperidine N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone; and N-(4-ethylbenzoyl)-pyrrolidine N'-(3,5-dimethylbenzoyl)-N'- t -butylhydrazone. A composition, which comprises a pesticidally effective amount of compound as claimed in any of claims 1 to 5, and an inert agronomically acceptable diluent or extender. A method of controlling pests, which comprises applying a pesticidally effective amount of a compound as claimed in any of claims 1 to 5, or a composition as claimed in claim 6, to a pest habitat or pest. A method as claimed in claim 7, wherein the pests are from the order Lepidoptera. Use of a compound as claimed in any of claims 1 to 5, or a composition as claimed in claim 6, to control pests, preferably pests from the order Lepidoptera.

Inventors: JACOBSON RICHARD MARTIN, JACOBSON, RICHARD MARTIN
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 1994
Main classification: C07C257
IPC codes: C07C327, A01N37, C07D295, C07C251, C07C313, A01N43, C07C257